CN105646755B - A kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization - Google Patents

A kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization Download PDF

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CN105646755B
CN105646755B CN201610046966.8A CN201610046966A CN105646755B CN 105646755 B CN105646755 B CN 105646755B CN 201610046966 A CN201610046966 A CN 201610046966A CN 105646755 B CN105646755 B CN 105646755B
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polymerization
catalyst
polyisoprene
rates
load
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CN105646755A (en
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于丽萍
谢忠
蔡杰
李连杰
付志凯
赵妍
张晓龙
徐伟伟
贾鹏冲
侯红霞
王玉强
陈双喜
王胜伟
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Shandong Yuhuang Chemical Co Ltd
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Jade Emperor Flourishing Age Chemical Inc Shandong
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F136/00Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F136/02Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F136/04Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F136/08Isoprene

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention discloses a kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization, using load-type Titanium series catalyst as major catalyst, aluminium agent is co-catalyst, third component is added into catalyst system, is catalyzed isoprene polymerization into the Crystalline plastics with trans Isosorbide-5-Nitrae structure.Third component and catalyst collective effect, improve and are catalyzed trans Isosorbide-5-Nitrae polyisoprene rate of polymerization, reduce the production cycle, reduce cost, there is provided a kind of TPI preparation methods of strong applicability.

Description

One kind improves anti-form-1, the method for 4- polyisoprene rates of polymerization
Technical field
The present invention relates to synthesis of polymer material rubber materials, and in particular to one kind improves anti-form-1,4- polyisoprene The method of rubber rate of polymerization.
Background technology
Anti-form-1,4- polyisoprene(TPI)Also known as artificial synthesized gutta-percha, both the strand with unsaturated rubber was soft It is pliable and can cure characteristics, there is the easy crystallinity of tacticity polymer again, thus can both show thermoplastic property, again Caoutchouc elasticity volume property can be showed.Double bond in its strand can be vulcanized;The compliance of chain is to may make up the base of elastomer Plinth;The order of trans configuration makes it easier to crystallize, and this is to cause it and natural rubber(NR)Different deciding factors.TPI The trans chain link identical period it is short, occur under normal temperature in the form of folded chain, less than 60 DEG C, i.e. rapid crystallization, is with high rigidity With the Crystalline plastics of high tensile.
TPI can be used as rubber elastomeric material, and the most outstanding feature of TPI vulcanizates is that rolling resistance is small, and heat is low, resistance to tired Labor and anti-wear performance are good.Research shows that the general purpose rubber such as TPI and NR, SBR, BR of synthesis has blending intervulcanizability energy well, When the mass fraction of TPI rubbers is 20% -30%, its blend compounds can not only keep every mechanical property of virgin rubber, and it is dynamic State property can improve significantly(Such as low-heat-generation, low-rolling-resistance, endurance), it is the preferable material for manufacturing High-performance green tire Material.In addition, TPI can be additionally used in other a variety of occasions as the substitute of gutta-percha, its main application fields is:1. artificial limb The medical function materials such as set, sports safety rehabilitation protector and brace;2. thermostimulation shape-memory material, such as special-shaped pipe joint, Multi-core cable joint, temperature detect switch (TDS) etc.;3. TPI and plastic blend, improve the processing characteristics of plastics.Gutta-percha have it is excellent into Film, film strength and air-tightness are very outstanding, available for the manufacture saturating radar wave encapsulant of air-tightness;4. golf coats Layer, insulating material, submarine cable etc..
The catalyst system of synthesis of trans-Isosorbide-5-Nitrae-polyisoprene mainly has vanadium system, vanadium/titanium mixed system, titanium system.
Vanadium system:The microstructure of most of catalyst system products therefrom is by catalyst proportion, temperature, solvent and additional The influence of the conditions such as electron donor is all insensitive, but polymerization speed is very slow, and polymer yield is at a fairly low.On its basis Modified catalyst, although although yield increases, increase rate is little, and contains mixing in obtained polymer Gel is not decomposed, the shortcomings of crystallinity and fusing point are relatively low.VOCl3/AlR3Obtained polymer is in relative molecular mass and has rule Lower than other halogenation vanadium on vertical structure, its anti-form-1,4- structural contents only have 90 % or so, it is difficult to prepare highly crystalline TPI.
Vanadium/titanium mixed system:This is a kind of improved catalysts that high trans structure TPI can be made, and with regard to polymerization speed, Also all it is higher for polymer yield and trans content.They can be divided into two types:One kind is heterogeneous system, including VCl3/TiCl3/AlEt3Three mutually mixes, or VCl3With AlEt3The system being deposited on together on titanium trichloride;Another kind is can Dissolubility system, it is made up of alkoxytitanium, trialkylaluminium and a kind of be carried on inert media vanadium trichloride.VCl3/ β-TiCl3/AlEt3Fast 50 times when average polymerization reaction rate caused by catalyst is than being used alone vanadium trichloride.But it is still Use solution polymerization process.
Titanium system:The Huang Bao treasures seminar of University Of Qingdao of China develops one kind and obtains supported titanium using mechanical lapping and urge Change the polymerization of isoprene bulk depositing, directly synthesize the new technology of TPI powders, be aggregated in N2Protection is lower to be carried out, according to Secondary addition isoprene, catalyst, lower stage feeding polymerization are stirred until complete monomer conversion is polymer beads, catalytic efficiency is more than 50 kg condensates/g Ti.With above-mentioned external vanadium system solution polymerization ratio, production technology is greatly simplified, and catalytic efficiency can improve 30 times or so, and energy and material consumption is greatly reduced, basic three-waste free discharge, therefore production cost is not only more much lower than foreign countries production TPI, Even than general containing intermingle with, method isoprene rubber is also low, is TPI popularization and application, and the application particularly in rubber tyre is created Condition.
In the prior art, solution polymerization process commercial synthesis anti-form-1, during 4- polyisoprene, due to its catalytic efficiency very Low, complex process, energy and material consumption height etc., price are higher than more than ten times of General Purpose Rubber, it is difficult to popularization and application.Therefore the present invention is for most There are the carrying catalyst in titanium series of the market competitiveness, especially MgCl2/TiCl4- triisobutyl aluminium catalyst system proposes increase The method of its rate of polymerization, and its truly feasible example is given, reduced the production cycle for commercial synthesis gutta-percha, increase production Amount, reduces cost.
The content of the invention
The present invention is solution the deficiencies in the prior art, there is provided one kind improves anti-form-1,4- polyisoprene rates of polymerization Method, reduce production cycle and cost.
The present invention is achieved through the following technical solutions:
One kind improves anti-form-1, and the method for 4- polyisoprene rates of polymerization, it is characterized in that:With load-type Titanium series Catalyst is major catalyst, and aluminium agent is co-catalyst, adds third component into catalyst system, catalysis isoprene polymerization into With anti-form-1, the Crystalline plastics of 4- structures;The third component is the elemental metals with reducing property.
The raising anti-form-1 of the present invention, the method for 4- polyisoprene rates of polymerization, the simple substance with reducing property Metal is preferably iron.
The raising anti-form-1 of the present invention, the method for 4- polyisoprene rates of polymerization, the load-type Titanium series catalyst are MgCl2Load TiCl4Type catalyst MgCl2/ TiCl4, its preparation method is ball-milling method, chemical method, ball milling and chemical combined method In one kind.
The raising anti-form-1 of the present invention, the method for 4- polyisoprene rates of polymerization, the polymerization methodses of isoprene are this Body precipitation polymerization, including prepolymerization, polymerization and devolatilization are dried;The pre-polymerization process is being sufficiently stirred lower progress, prepolymerization temperature Spend for-15-5 DEG C, prepolymerization time 0.5-10h;The polymerization process is being sufficiently stirred lower progress, polymerization process addition chain Transfer agent, polymerization temperature are 10-35 DEG C, polymerization time 10-40h;The chain-transferring agent is hydrogen, is led to when polymerizeing and starting Enter, the pressure for being passed through hydrogen is 0.001-1 MPa.
The raising anti-form-1 of the present invention, the method for 4- polyisoprene rates of polymerization, operation are as follows:Anoxybiotic, exhausted water, absolutely Under conditions of impurity, first two container single port bottles are cleaned, dry, vacuumized, use N2For several times, one of bottle is taken out for displacement Vacuum, and add isoprene monomer and quantitative AlR3, another bottle adds major catalyst and different types of reproducibility Fe element simultaneously vacuumizes;By isoprene monomer and AlR3The bottle equipped with major catalyst and iron element is added under stirring In son, it is being sufficiently stirred lower stage feeding polymerization and is being passed through the hydrogen of certain pressure, is finally being terminated with the ethanol solution equipped with stabilizer Polymerization;Resulting polymers particle is dried to constant weight in vacuum drying chamber, weighs and calculates conversion ratio, catalytic efficiency, test Its trans content, Mooney;Polymerizing condition is:Ti/Ip>2.5×10-6(mol ratio, similarly hereinafter), Al/Ti 10-300, fe can Think iron wire, iron powder, iron block, nanometer iron powder, reproducibility iron powder, and the material containing fe such as magnet.
The beneficial effects of the invention are as follows:The present invention adds the third component metal with reducing property in catalyst system Simple substance, catalysis anti-form-1 is improved, 4- polyisoprene rates of polymerization, the production cycle is reduced, reduces cost, there is provided one kind is applicable The strong TPI preparation methods of property.
Embodiment
Embodiment 1
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Displacement for several times and numbering 1,2, by 1 Number bottle adds catalyst MgCl2/ TiCl4, rotor and reduced iron powder and vacuumize, No. 2 bottles vacuumize, and add isoamyl two Alkene monomer and quantitative AlR3, mol ratio Ti/Ip=1.25 × 10 of Ti and isoprene-4, Al and Ti mol ratios Al/Ti=60, By isoprene monomer and AlR in No. 2 bottles3, No. 1 equipped with catalyst, rotor and reduced iron powder is added under stirring In bottle, lower stage feeding polymerization is being sufficiently stirred, polymerization time 20 hours, polymerization is being terminated with the ethanol solution equipped with stabilizer.Will Resulting polymers particle is dried to constant weight in vacuum drying chamber, and isoprene conversion ratio is 28 %, catalytic efficiency 3.246 kg/g Ti。
Comparative example 1
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Replace for several times and number, by headpin Son adds catalyst and rotor and vacuumized, and No. 2 bottles vacuumize, and add isoprene monomer and quantitative AlR3, Ti with Mol ratio Ti/Ip=1.25 × 10 of isoprene-4, Al and Ti mol ratios Al/Ti=60, by isoprene monomer in No. 2 bottles and AlR3, it is added under stirring in headpin equipped with catalyst and rotor, is being sufficiently stirred lower stage feeding polymerization, is polymerize 20 hours time, polymerization is terminated with the ethanol solution equipped with stabilizer.Resulting polymers particle is dried in vacuum drying chamber To constant weight, isoprene conversion ratio is 2.201 %, and catalytic efficiency is 255 g/g Ti.
Embodiment 2
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Replace for several times and number, by headpin Son adds catalyst, rotor and thin wire simultaneously vacuumize, and No. 2 bottles vacuumize, and adds isoprene monomer and quantitative AlR3, mol ratio Ti/Ip=1.25 × 10 of Ti and isoprene-4, Al and Ti mol ratios Al/Ti=150, by isoamyl in No. 2 bottles Diene monomers and AlR3, it is added under stirring in headpin equipped with catalyst, rotor and thin wire, is fully stirring Lower stage feeding polymerization is mixed, polymerization time 20 hours, polymerization is terminated with the ethanol solution equipped with stabilizer.Resulting polymers particle is existed It is 168.7 to be dried in vacuum drying chamber to constant weight, test Mooney.
Comparative example 2
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Replace for several times and number, by headpin Son adds catalyst and rotor and vacuumized, and No. 2 bottles vacuumize, and add isoprene monomer and quantitative AlR3, Ti with Mol ratio Ti/Ip=1.25 × 10 of isoprene-4, Al and Ti mol ratios Al/Ti=150, by isoprene monomer in No. 2 bottles and AlR3, add and be equipped with catalyst and rotor headpin under stirring, be sufficiently stirred lower stage feeding polymerization, polymerization time 20 hours, polymerization is terminated with the ethanol solution equipped with stabilizer.Resulting polymers particle is dried to perseverance in vacuum drying chamber Weight, test Mooney are 152.6.
Embodiment 3
First two 500 ml container single port bottles are cleaned, dry, vacuumized, with pure N2Replace for several times and number, by headpin Son adds catalyst, rotor and thin wire simultaneously vacuumize, and No. 2 bottles vacuumize, and adds isoprene monomer and quantitative AlR3, mol ratio Ti/Ip=1.25 × 10 of Ti and isoprene-4, Al and Ti mol ratios Al/Ti=120, by isoamyl in No. 2 bottles Diene monomers and AlR3, it is added under stirring in headpin equipped with catalyst, rotor and thin wire, is fully stirring Lower stage feeding polymerization is mixed, polymerization time 20 hours, polymerization is terminated with the ethanol solution equipped with stabilizer.Resulting polymers particle is existed It is 152.8 to be dried in vacuum drying chamber to constant weight, test Mooney.

Claims (5)

1. one kind improves anti-form-1, the method for 4- polyisoprene rates of polymerization, it is characterised in that:With load-type Titanium series catalyst For major catalyst, aluminium agent is co-catalyst, third component is added into catalyst system, catalysis isoprene polymerization is into anti- The Crystalline plastics of formula-Isosorbide-5-Nitrae-structure;The third component is the fe with reducing property.
2. raising anti-form-1 according to claim 1, the method for 4- polyisoprene rates of polymerization, it is characterised in that:Institute It is MgCl to state load-type Titanium series catalyst2Load TiCl4Type catalyst MgCl2/ TiCl4, its preparation method is ball-milling method, chemistry One kind in method, ball milling and chemical combined method.
3. raising anti-form-1 according to claim 1, the method for 4- polyisoprene rates of polymerization, it is characterised in that:It is different The polymerization methodses of pentadiene are bulk precipitation polymerization, including prepolymerization, polymerization and devolatilization are dried.
4. raising anti-form-1 according to claim 3, the method for 4- polyisoprene rates of polymerization, it is characterised in that:Institute It is-15-5 DEG C that pre-polymerization process, which is stated, being sufficiently stirred lower progress, prepolymerization temperature, prepolymerization time 0.5-10h;It is described poly- Conjunction process is being sufficiently stirred lower progress, and polymerization process addition chain-transferring agent, polymerization temperature is 10-35 DEG C, polymerization time 10- 40h。
5. raising anti-form-1 according to claim 4, the method for 4- polyisoprene rates of polymerization, it is characterised in that:Institute It is hydrogen to state chain-transferring agent, is passed through when polymerizeing and starting, the pressure for being passed through hydrogen is 0.001-1 MPa.
CN201610046966.8A 2016-01-25 2016-01-25 A kind of method for improving trans Isosorbide-5-Nitrae polyisoprene rate of polymerization Active CN105646755B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB840165A (en) * 1958-04-28 1960-07-06 Goodyear Tire & Rubber Method of preparing 1,4 trans polyisoprene
CN1425699A (en) * 2001-12-12 2003-06-25 黄宝琛 Synthesis of medium and low relative molecular mass trans-1,4-polyisoprene wax and trans-1,4-poly butadiene wax
CN1847272A (en) * 2006-04-11 2006-10-18 青岛科大方泰材料工程有限公司 Industrial synthesis process of high trans-1, 4-iroprene polymer

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB840165A (en) * 1958-04-28 1960-07-06 Goodyear Tire & Rubber Method of preparing 1,4 trans polyisoprene
CN1425699A (en) * 2001-12-12 2003-06-25 黄宝琛 Synthesis of medium and low relative molecular mass trans-1,4-polyisoprene wax and trans-1,4-poly butadiene wax
CN1847272A (en) * 2006-04-11 2006-10-18 青岛科大方泰材料工程有限公司 Industrial synthesis process of high trans-1, 4-iroprene polymer

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